Sensitized silver halide emulsion containing a halogenated triazine as sensitizer and a halogenated compound hardening agent

ABSTRACT

wherein R1, R2 and R3 each represent a hydroxyl group, a hydroxylamino group, an amino group, an alkylamino group of from 1-6 carbon atoms, said alkyl group of said alkylamino group capable of being substituted by a member selected from the group consisting of a hydroxy group, a dialkylamino group of from 2 to 8 carbon atoms and an alkoxy group of from 1 to 4 carbon atoms, an arylamino group, said arylamino group capable of being substituted with a member selected from the group consisting of an alkyl group of from 1 to 4 carbon atoms, an alkoxy group of from 1 to 4 carbon atoms, a hydroxy group and a halogen atom, an alkoxyl group of from 1 to 6 carbon atoms, an aryloxy group, said aryloxy group capable of being substituted with a member selected from the group consisting of an alkyl group of from 1 to 4 carbon atoms, an alkoxy group of from 1 to 4 carbon atoms, a hydroxy group, and a halogen atom, an alkyl group of from 1 to 6 carbon atoms, an aryl group, said aryl group capable of being substituted with a member selected from the group consisting of an alkyl group of from 1 to 4 carbon atoms, an alkoxy group of from 1 to 4 carbon atoms, a hydroxy group, and a halogen atom, or a halogen atom, said compound represented by the above described formula containing no more than one group which is active to gelatin, with the proviso that if R1, R2 or R3 is a halogen atom, no more than one of said R1, R2 and R3 can be a halogen atom. The uniqueness of the above-described invention resides in the fact that the compounds set forth above, do not exhibit a hardening effect on gelatin, but rather, exhibit a sensitizing effect when employed in a gelatino silver halide photo-sensitive material. A practical, useful gelatino silver halide photo-sensitive material having incorporated therein a compound represented by the following formula:

United States Patent [1 1 Ohtani et al.

[ SENSITIZED SILVER HALIDE EMULSION CONTAINING A HALOGENATED TRIAZINE AS SENSITIZER AND A HALOGENATED COMPOUND HARDENING AGENT [75] Inventors: Katsuhiko Ohtani; Yosuke Nakajima; Reiichi Ohi, all of Minami-ashigara, Japan; Tokiharu Kondo, deceased, late of Odawara, Japan, by Yoshiharu Kondo, legal representative [73] Assignee: Fuji Photo Film C0,, Ltd., Minamiashigara, Japan [22] Filed: July 13, 1973 [2i] Appl. No: 378,845

Related US. Application Data [63] Continuation-in-part of Ser. No. 74,520, Nov. 2,

I970, abandoned.

[30] Foreign Application Priority Data Sept, 22, I972 Japan 47-75467 [52] US. Cl. 96/107; 96/108; 96/111 [51] Int. Cl. G03C 1/28 [58] Field of Search 96/11], I07, 109, 108

{56] References Cited UNITED STATES PATENTS 3,502,477 3/l970 Ohi et al. l 96/109 3,549,377 l2/l970 Meckl et al 96H ll Primary Examiner-Won H. Louie, Jr, Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn and Macpeak [57] ABSTRACT A practical, useful gelatino silver halide photosensitive material having incorporated therein a compound represented by the following formula:

[4 1 Sept. 16, 1975 wherein R,, R and R each represent a hydroxyl group, a hydroxylamino group, an amino group, an alkylamino group of from l-6 carbon atoms, said alkyl group of said alkylamino group capable of being substituted by a member selected from the group consisting of a hydroxy group, a dialkylamino group of from 2 to 8 carbon atoms and an alkoxy group of from l to 4 carbon atoms, an arylamino group, said arylamino group capable of being substituted with a member selected from the group consisting of an alkyl group of from 1 to 4 carbon atoms, an alkoxy group of from I to 4 carbon atoms, a hydroxy group and a halogen atom, an alkoxyl group of from I to 6 carbon atoms, an aryloxy group, said aryloxy group capable of being substituted with a member selected from the group consisting of an alkyl group of from 1 to 4 carbon atoms, an alkoxy group of from l to 4 carbon atoms, a hydroxy group, and a halogen atom, an alkyl group of from I to 6 carbon atoms, an aryl group, said aryl group capable of being substituted with a member selected from the group consisting of an alkyl group of from I to 4 carbon atoms, an alkoxy group of from I to 4 carbon atoms, a hydroxy group, and a halogen atom, or a halogen atom, said compound represented by the above described formula containing no more than one group which is active to gelatin, with the proviso that if R,, R or R is a halogen atom, no more than one of said R R and R can be a halogen atom.

The uniqueness of the above-described invention resides in the fact that the compounds set forth above, do not exhibit a hardening effect on gelatin, but rather, exhibit a sensitizing effect when employed in a gelatino silver halide photo-sensitive material.

8 Claims, No Drawings SENSITIZED SILVER I-IALIDE EMULSION CONTAINING A HALOGENATED TRIAZINE AS SENSITIZER AND A HALOGENATED COMPOUND HARDENING AGENT CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part application of our earlier co-pending application Ser. No. 74,520 filed on Nov. 2, 1970, now abandoned and claims priority from Japanese Pat. Application No. 75,467/69, filed Sept. 22, 1969.

BACKGROUND OF THE INVENTION l. Field of the invention The present invention relates to a gelatino silver halide photo-sensitive material, and more particularly, to a practical and useful gelatino silver halide photosensitive material containing a compound to effect both the sensitization, due to the increase of the covering power based on control of the hardening, and to prevent the formation of fog.

2. Description of the Prior Art In the hitherto known production ofsuch gelatino silver halide photo-sensitive material, there have been proposed a great variety of processes to increase the sensitivity and the gamma of the photo-sensitive material, for example, by adding a covering powerincreasing agent, for example, natural or synthetic high molecular weight compounds, such as poly-N- vinylpyrrolidone, dextrin, laminarin, mannam, hydroxyethylated cellulose, and the like.

The addition of these compounds makes it possible to effect an increase in the ratio of the optical density of silver to the weight of silver, namely, covering power and increase of contrast.

Generally, the addition of a large quantity of high molecular weight compounds is required; however, this has the disadvantages that the time necessary for development is increased due to the increased thickness of the emulsion layer as well as the adverse effects on the physical strength of the gelatin underlayer.

A primary object of the present invention is to provide a silver halide photosensitive material with increased sensitivity, maximum density and contrast based on an increase in covering power.

It is another object of the present invention to provide a photosensitive material having a shorter developing time than that of known photo-sensitive materials containing a covering power-increasing agent while preventing a decrease of the physical strength of the gelatin layer.

SUMMARY OF THE INVENTION The above purposes of the present invention are achieved by incorporating a suitable quantity ofa compound represented by the following Formula (I) into a gelatino silver halide emulsion sensitized to its maximum sensitivity by a conventional chemical sensitization process, for example, a reduction sensitization. a sulfur sensitization, a gold sensitization or combination thereof:

Formula (I):

wherein R R and R each represent a hydroxy] group, a hydroxylamino group, an amino group, an alkylamino group of from l6 carbon atoms, said alkyl group of said alkylamino group capable of being substituted by a member selected from the group consisting of a hycl'roxy group, a dialkylamino group of from 2 to 8 carbon atoms and an alkoxy group of from I to 4 carbon atoms, an arylamino group, said arylamino group capable of being substituted with a member selected from the group consisting of an alkyl group of from 1 to 4 carbon atoms, an alkoxy group of from I to 4 carbon atoms, a hydroxy group and a halogen atom, an alkoxyl group of from I to 6 carbon atoms, an aryloxy group, said aryloxy group capable of being substituted with a member selected from the group consisting of an alkyl group of from I to 4 carbon atoms, an alkoxy group of from I to 4 carbon atoms, a hydroxy group, and a halo gen atom, an alkyl group of from I to 6 carbon atoms, an aryl group, said aryl group capable of being substi tuted with a member selected from the group consisting of an alkyl group of from I to 4 carbon atoms, an alkoxy group of from I to 4 carbon atoms, a hydroxy group, and a halogen atom, or a halogen atom, said compound represented by the above-described formula containing no more than one group which is active to gelatin, with the proviso that if R R and R is a halogen atom, no more than one of said R,, R and R can be a halogen atom.

Illustrative of suitable alkylamino groups, are such groups as methylamino, dimethylamino, ethylamino, diethylamino, propylamino, butylamino, and the like; illustrative of a substituted alkylamino group, is a hydroxyalkylamino group; illustrative of suitable arylamino groups are those of phenylamino, naphthylamino and the like; illustrative of suitable alkoxyl groups are those of methoxy, ethoxy. propoxy and the like; illustrative of suitable aryloxy groups are those of phenoxy, naphthoxy and the like; illustrative of suitable alkyl groups are those of methyl, ethyl, propyl and the like; illustrative of suitable aryl groups are those of phenyl, naphthyl and the like; and finally, illustrative of suitable halogen atoms are those of chlorine, bromine, fluorine or iodine.

Naturally, the amount of sensitizing compound, as described above, to be added to a gelatino silver halide photographic emulsion will vary, especially depending upon the amount of hardening agent employed. Therefore, all that is generally required, is that a sufficient amount of compound be present so as to exhibit or exert a sensitizing effect. Normally. an amount in the range of from ().()l to I00 grams per mole of silver halide is suitable.

DESCRIPTION OF THE PREFERRED EMBODIMENTS While the addition of the compound of the present invention somewhat lowers the hardening property, a photo-sensitive material having a gelatin layer with enough strength for practical use can be obtained by suitable control of the quantity of hardening agent added.

The preferred hardening agents applicable to the present invention are selected especially from those NHC C-NHOH having an active halogen, e.g., those of the mucohaloic 5 l N N acid type, such as mucochlonc acld, mucobromic acid, those of the halodiazine and halotriazine type, such as 2,4-dichloro-6-hydroxy-l,3,5-triazine sodium salt and the like. Suitable examples of hardening agents of the mucohaloic acid type are described in US. Pat. No. 10 11100 2983,61 1, US. Pat. No. 3,325,287, US. Pat. No. cgmpound 3,549,377, British Pat. No. 1,072,008 and British Pat. No. 1,193,290; while suitable examples of halodiazine and halotriazine type hardening compounds can be found in us. Pat. No. 2,080,019, us. Pat. No. 3,579,374 and Belgian Pat. No. 725,964. Also, the use I H of other aldehyde and epoxy type hardening agents N N may be effectlve. c

The amount of the hardening agent used in the pres- L ent invention is from 0.5 milli mole to 10 milli mole, preferably from 4.5 milli mole to 5 milli mole, per Kg m p 250C of emulsion,

Stabilizers and coating aids may also be employed in the present invention, such as tetrazaidene type stabi- Compound 6:

lizers and saponin type coating aids. N

Several embodiments of the compound represented C H NHOH by the above formula which may be practically used in 2 a i I the present invention include the following com N N pounds. These compounds may be used individually or in mixtures thereof, and the present invention should I not be limited to the following specific compounds: NHOH Compound 1:

m.p. 208 210C. Compound 7:

C,H ,NH C C-NHOH CHs N C2:

C c H N N c H m I 3 2 B 1LHC,H N,

| m.p. |94 196C. Compound 2:

b.p. 1s3- 6C/4.5 mmHg Compound 8: Cm, //N

\N-C \C -NHOH N I ll z s N N C|H5OC CNH C N rL cgHn \\C/ 'z n m.p. 146- 147C. Compound 3: m.p. 1 10 114C.

Compound 9:

HONH-(f tf-NHOH N N @a, C NN, N N c,n, 1

m.p. C.

Compound 4: m.p. 181 182C.

m.p. 9798C.

The synthesis of these compounds can be easily achieved by reaction of chloro-S-triazine or its derivative with the corresponding amines, phenols and/or a1- cohols.

Methods of synthesis of the compounds of the present invention have been worked out according to various methods as described in the prior art, for example, Journal of the American Chemical Society, Vol. 73, Page 298| and Journal of Organic Chemistry, Vol. 27, Page 4054.

A typical example of synthesis will be illustrated as follows:

EXAMPLE OF SYNTHESIS OF COMPOUND l A solution of 922g. of cyanuric trichloride dissolved in 200 ml. of dioxane was added to 300 ml. of water with stirring to prepare a slurry, which was then cooled to 5C. After adding dropwise 64.4g. ofa 70% aqueous ethyl amine solution, the system was heated to 40C., and 300 ml. of an aqueous solution containing 40g. of caustic soda was dropwise added thereto to adjust the pH of the reaction mixture to neutrality.

The crystals deposited after 4 hours were filtered off and washed with water. i

A solution of 140g. of hydroxylamine hydrochloride dissolved in 300 ml. of water was cooled to lower than 20C., and mixed, while passing N gas through the solution, with l70 ml. of an aqueous solution containing 80g. of caustic soda to neutralize the solution, and 500 ml. of dioxane having suspended therein the above crystals was added thereto.

The resulting mixture was then allowed to react for 30 minutes at 50C., and further for 4 hours at 85C.

The reactant solution was cooled, after filtering off insoluble matter, to precipitate crystals. The precipitated crystals were filtered off and recrystallized from methanol to obtain the object crystalline compound melting at l97l98C. The synthesis of Compounds Nos. 2-4, 7 and were conducted using the corresponding amine in a manner similar to the process of making Compound 1.

Compounds 8 and 9 could be produced from the corresponding amine and alcohol or phenol, and similarly, Compound 5 from 2-phenyl-4,6-dichloro-1 ,3,5-triazine synthesized in accordance with a method as in the Journal of the American Chemical Society, Vol. 60, page 1657, and Compound 6 from a 2-ethyl derivative.

These compounds can be added to the emulsion in methanol solution or in hydrochloric aqueous solution.

The period of time over which the compound is added to the emulsion is not especially limited, but it is advantageous to perform the addition subsequent to ripcning" thereof but prior to the coating.

There is no particular limitation in the use of specific silver halide compositions in the emulsion, for purposes of the present invention.

Variations in the (i unity of the compound used in the present invention are usually dependent upon the kind of hardening agent used therewith, and good results can be obtained by the addition of the compound in a quantity of 0.05O.5g. per l milli mole ofthe hardening agent.

The support used in the present invention may be selected from those which are conventionally utilized, the particular support not being limited for purposes of the present invention.

That is to say, even if well-known supports, for example, film bases such as polyester film, cellulose triacetate film; dry plate; paper bases such as baryta paper, resin laminated paper, synthetic paper, and metallic plate, etc., are utilized, any one of them is suitable to obtain an effective product.

The following examples will serve more specifically to set forth the present invention, it being understood that the following examples are merely illustrative, and not limiting, in nature.

EXAMPLE 1:

4-hydroxy-6-methyl-1,3,3a, 7-tetrazaidene and saponin were added to a gelatino silver iodobromide emulsion (molar ratio; Agl AgBr 1.5 98.5) used for a highly sensitive X-ray and was sensitized with both so dium thiosulfate and gold chloride.

The resultant emulsion was mixed with 5 milli mole of mucochloric acid per Kg of emulsion as a hardening agent and various amounts of Compound 1 according to the present invention, then each mixture was coated onto a polyethylene terephthalate base, and dried to a thickness of 5.6 1..

Each sample was exposed through a blue filter to a 5400K light source for l/20 second, developed in a high pH phenidone-hydroquinone developer used for Xray film. The results are shown in Table 1.

From Table I, it is clear that the sensitivity and the gamma were increased and the fog was lowered by the addition of the compound of the present invention when compared to the sample tested without the compound of the present invention.

The gamma and the fog were equivalent to those values obtained under developing conditions of 40C. for 25 seconds.

TABLE 1 Amount of Specific Gamma Fog Compound I Sensitivity (g/Kg emulsion) 0 I00 I (H7 025 [I5 L97 0.16 0.5 ll2 2.30 (H6 EXAMPLES 2-5:

TABLE 2 Ex. Amount of Specific Nos. Compound Compound Sensiti- (yKg emulsion] vity Fog amma None lot) L70 0.20 Polyvinyl pyrrolidone 0.5 1 l2 L80 0.23 (comparison) 2 Compound I I55 2.50 0J8 3 Compound 2 I02 1.80 0,08 4 Compound 3 I60 2.52 0.20 5 Compound 7 H0 L80 0.16

From the results shown in Table 2, it can be seen that by adding a compound of the present invention, as compared with no additive or a conventional additive, a higher sensitivity and fog and a lower fog are obtained.

Although the present invention has been adequately described and set forth in the foregoing specification and Examples included therein, it is readily apparent that various changes and modifications can be made, by the skilled artisan, without departing from the spirit and scope thereof.

What is claimed is:

l. A gelatino silver halide photo-sensitive emulsion which comprises, a silver halide emulsion sensitized to its maximum sensitivity by conventional chemical sen sitization containing a sensitizing effective amount of a sensitizing compound represented by the following formula:

wherein R R and R each represent a hydroxyl group, a hydroxylamino group, an amino group, an alkylamino group of from l-6 carbon atoms, said alkyl group of said alkylamino group capable of being substituted by a member selected from the group consisting of a hydroxy group, a dialkylamino group of from 2 to 8 carbon atoms and an alkoxy group of from 1 to 4 carbon atoms, an arylamino group, said arylamino group capable of being substituted with a member selected from the group consisting of an alkyl group of from 1 to 4 carbon atoms, an alkoxy group of from 1 to 4 carbon atoms, a hydroxy group and a halogen atom, an alkoxyl group of from I to 6 carbon atoms, an aryloxy group, said aryloxy group capable of being substituted wih a member selected from the group consisting of an alkyl group of from I to 4 carbon atoms, an alkoxy group of from 1 to 4 carbon atoms, a hydroxy group, and a halogen atom, an alkyl group of from 1 to 6 carbon atoms, an aryl group, said aryl group capable of being substituted with a member selected from the group consisting of an alkyl group of from to 4 carbon atoms, an alkoxy group of from l to 4 carbon atoms, a hydroxy group, and a halogen atom, or a halogen atom, said compound represented by the above described formula containing no more than one group which is active to gelatin, with the proviso that if R,, R or R is a halogen atom, no more than one of said R R and R;, can be a halogen atom, and an organic hardening agent having an active halogen.

2. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the alkylamino group is methylamino, dimethylamino, ethylamino, diethylamino, propylamino or butylarnino', wherein the substituted alkylamino group is hydroxyalkylamino; wherein the arylamino group is phenylamino or naphthylamino; wherein the alkoxyl group is methoxy, ethoxy or propoxy; wherein the aryloxy group is phenoxy or naphthoxy; wherein the alkyl group is methyl, ethyl or propyl; wherein the aryl group is phenyl or naphthyl; and wherein the halogen is chlorine, bromine, fluorine or iodine.

3. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the sensitizing compound is selected from the group consisting of:

4. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the hardening agent is selected from the group consisting of mucochloric acid, mucobromic acid and 2,4-dichloro-6-hydroxyl ,3,5- triazine sodium salt.

5. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the amount of hardening agent varies from 0.5 milli mole to 10 milli mole per Kg of emulsion.

9 l 6. The gelatino silver halide photo-sensitive emulsion I0.0g. per mole of silver halide present. as Claimed in Claim 1 wherein the amount of Said 8. A gelatino silver halide photo-sensitive material pound varies from 0.05g. to 0.5g. per milli mole of said hardening agent.

7. The gelatino silver halide photo sensitive emulsion 5 contalmng the sllver halide photo-sensitive emulsion as as claimed in claim 1, wherein the amount of said sensiclaimed in Claim tizing compound ranges from about 0.0lg. to about comprising a support having thereon at least one layer UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,905,821 D TE 1 September 16, 1975 INVENTOR( I Katsuhiko OHTANI et a1 It is certified that error appears in the ab0ve-identified patent and that said Letters Patent are hereby corrected as shown below:

Under "Foreign Application Priority Data",

Delete "Sept. 22, 1972" and insert "Sept. 22, 1969";

AND

Delete "4775467" and insert "44-75467" Signed and Scaled this twentieth D f January I 976 [SEAL] A ttes r: 

1. A GELATINO SILVER HALIDE PHOTO-SENSITIVE EMULSION WHICH COMPRISES, A SILVER HALIDE EMULSION SENSITIZED TO ITS MAXIMUM SENSITIVITY BY CONVENTIONAL CHEMICAL SENSITIZATION CONTAINING A SENSITIZING EFFECTIVE AMOUNT OF A SENSTIZING COMPOUND REPRESENTED BY THE FOLLOWING FORMULA:
 2. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the alkylamino group is methylamino, dimethylamino, ethylamino, diethylamino, propylamino or butylamino; wherein the substituted alkylamino group is hydroxyalkylamino; wherein the arylamino group is phenylamino or naphthylamino; wherein the alkoxyl group is methoxy, ethoxy or propoxy; wherein the aryloxy group is phenoxy or naphthoxy; wherein the alkyl group is methyl, ethyl or propyl; wherein the aryl group is phenyl or naphthyl; and wherein the halogen is chlorine, bromine, fluorine or iodine.
 3. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the sensitizing compound is selected from the group consisting of:
 4. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the hardening agent is selected from the group consisting of mucochloric acid, mucobromic acid and 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt.
 5. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the amount of hardening agent varies from 0.5 milli mole to 10 milli mole per Kg of emulsion.
 6. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1 wherein the amount of said compound varies from 0.05g. to 0.5g. per milli mole of said hardening agent.
 7. The gelatino silver halide photo-sensitive emulsion as claimed in claim 1, wherein the amount of said sensitizing compound ranges from about 0.01g. to about 10.0g. per mole of silver halide present.
 8. A gelatino silver halide photo-sensitive material comprising a support having thereon at least one layer containing the silver halide photo-sensitive emulsion as claimed in claim
 1. 